NL2031224B1 - Underway multi-parameter seawater acidification observer - Google Patents

Underway multi-parameter seawater acidification observer Download PDF

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Publication number
NL2031224B1
NL2031224B1 NL2031224A NL2031224A NL2031224B1 NL 2031224 B1 NL2031224 B1 NL 2031224B1 NL 2031224 A NL2031224 A NL 2031224A NL 2031224 A NL2031224 A NL 2031224A NL 2031224 B1 NL2031224 B1 NL 2031224B1
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Netherlands
Prior art keywords
sample
dic
peristaltic pump
seawater
detector
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NL2031224A
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Dutch (nl)
Inventor
Zhang Miming
Lin Qi
Yan Jinpei
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Third Institute Of Oceanography Mini Of Natural Resources Prc
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/18—Water

Abstract

An underway multi—parameter seawater acidification observer is disclosed, relating to the technical field of ocean monitoring, wherein sample outlets of a seawater filter and a standard liquid storage tank are respectively connected, to sample inlets of a three—way valve, a sample outlet of the three—way valve is connected, to a sample inlet of a liquid, dispenser, two sample outlets of the liquid dispenser are respectively connected to sample inlets of a first peristaltic pump and a second peristaltic pump, a sample outlet of the first peristaltic pump is connected to a sample inlet of a flow—through cell, and a sample outlet of the second peristaltic pump is connected to a sample inlet of a DIC detector; a water purifier is connected to a carrier sample inlet of the DIC detector through a constant flow pump; and a pH probe extends into the flow—through cell.

Description

P1221 /NLpd
UNDERWAY MULTI-PARAMETER SEAWATER ACIDIFICATION OBSERVER
TECHNICAL FIELD
The present invention relates to the field of marine monitor- ing technology, and in particular to an underway multi-parameter seawater acidification observer.
BACKGROUND ART
The pH and DIC in seawater are important parameters to char- acterize the acidification of seawater, and are important indica- tors in the study of ocean acidification, which have become the basic parameters in the study of marine acidification and are im- portant parameters to understand the process of marine biological activities and response thereof to marine environment. The accu- rate, rapid and convenient determination of the spatio-temporal distribution and variability of seawater pH and DIC concentration with high spatio-temporal resolution is an indispensable key pa- rameter for the study of marine biogeochemical processes and plays an important role in the global marine ecosystem research for un- derstanding ocean acidification and the impact on marine biologi- cal activities.
Seawater acidification is mainly caused by the dissolution of
CO:, so dissolved inorganic carbon (DIC) in seawater is a key pa- rameter for studying seawater acidification. Coulometric titration is currently the main analytical method for DIC determination. As the current and time parameters can be accurately controlled, this method can achieve high accuracy and precision, and the general analysis error is about 0.05%, which is often used as a standard method for DIC determination. However, Coulometric titration is only suitable for laboratory operation and cannot be used for on- site analysis and determination at sea due to its time-consuming measurement and the huge volume of the entire analysis system.
With the development of technology, new methods and new princi- ples-based analytical techniques have emerged in recent years around the determination of DIC, TA and pH of seawater. Sayles et.al. measured DIC using a three-electrode conductivity detector by acidifying a seawater sample to allow CO: to escape through a silicone semipermeable membrane and be absorbed by a dilute NaOH solution. In order to ensure the measurement accuracy, multi-point standard samples were used for calibration, the measurement accu- racy of DIC concentration in a range of 1.6-2.8 mM was + 5 pM, and the analysis time of single sample was about 70 min. The major drawbacks of this method are long time consumption and high con- sumption of chemical reagents. Pencharee et.al. developed a DIC measurement device using a non-contact conductivity detector with a flow injection gas diffusion technology. The measurement accura- cy was 0.48%, with a concentration linear range of 0.2-10 mM. Both the power consumption and volume of the detector used in this method were large, and the measurement accuracy of 0.48% was ob- tained at the concentration of 6 mM DIC; at present, the average concentration of DIC in the great ocean ranges from 1.8-2.3 mM, and in sea areas with high DIC, such as the Black Sea, it is only 3.8-4.3 mM. At present, the measurements of pH and DIC are mostly independent, and there is no multi-parameter synchronous observa- tion instrument. Since the four parameters for seawater acidifica- tion, such as pH, DIC, alkalinity and calcium ion, have correla- tion, any two parameters can be obtained by calculating the other two parameters.
At present, the instruments and equipment for observation of seawater acidification still rely on import, and the backward field measurement technology cannot get a lot of accurate field observation data. In order to improve the overall level of carbon cycle and ocean acidification research in China, it is urgent to improve the on-site measurement technology of ocean acidification in China, and establish a multi-parameter (DIC, pH, temperature, salinity) ocean acidification automatic observation system with high precision, low cost and in-situ measurement.
SUMMARY
The object of the present invention is to solve the above- mentioned problems in the prior art of single seawater acidifica- tion observation parameter, being unable to perform multi-
parameter synchronous observation, complicated analysis method, and consuming a large amount of manpower and material resources, an underway multi-parameter seawater acidification observer is provided, which can automatically observe the acidification param- eters such as pH and DIC of seawater for a long time.
In order to achieve the above object, the present invention adopts the following technical solution: an underway multi- parameter seawater acidification observer comprises a seawater filter, a standard liquid storage tank, a three-way valve, a liqg- uid dispenser, a first peristaltic pump, a flow-through cell, a pH probe, a pH probe detection circuit, a second peristaltic pump, a
DIC detector, a constant flow pump, a water purifier, a data ac- quisition and control chip, and a computer; sample outlets of the seawater filter and the standard liquid storage tank are respec- tively connected to the sample inlets of the three-way valve, a sample outlet of the three-way valve is connected to a sample in- let of the liquid dispenser, two sample outlets of the liquid dis- penser are respectively connected to sample inlets of the first peristaltic pump and the second peristaltic pump, a sample outlet of the first peristaltic pump is connected to a sample inlet of the flow-through cell, and a sample outlet of the second peristal- tic pump is connected to a sample inlet of the DIC detector; the water purifier is connected to a carrier sample inlet of the DIC detector through a constant flow pump; the pH probe extends into the flow-through cell, and the pH probe is electrically connected to a pH probe detection circuit; the three-way valve, the first peristaltic pump, the second peristaltic pump, the pH probe detec- tion circuit, the DIC detector, the constant flow pump and the circuit of the water purifier are all connected to a data acquisi- tion and control chip, and the data acquisition and control chip is connected to a computer so as to control the automatic sampling and detection of the instrument via the data acquisition and con- trol chip.
The carrier sample outlet of the DIC detector is connected to the water purifier to recycle the measured carrier waste liquid. A parameter measurement method for the underway multi-parameter sea- water acidification observer comprises the following steps: during the measurement of the seawater sample, the valve position of the three-way valve is switched to the seawater sample inlet for sam- ple injection, firstly, the seawater sample passes through a fil- ter to remove suspended seawater particles, and the seawater sam- ple is divided into two paths via a liquid dispenser, wherein one path is conveyed to a flow-through cell by a first peristaltic pump, and parameters such as pH, temperature and salinity of the sample are measured by a pH probe, and the other path is conveyed to a DIC detector by a second peristaltic pump to measure a DIC concentration of the sample; the detection time interval of pH probe and DIC detector are set as required, so as to realize the synchronous measurement of different parameters.
Before the seawater sample is measured, the standard curve is made and the instrument is calibrated in the present invention. In the present invention, a method for making the standard curve and calibrating the instrument is as follows: firstly, the valve posi- tion of the three-way valve is switched to the standard sample in- let by a control system, after the standard solution enters the three-way valve through a standard solution storage tank, the standard sample is divided into two paths through a liquid dis- penser, wherein one path enters a flow-through cell through a first peristaltic pump, and parameters such as pH, temperature and salinity of the standard sample are measured by a pH probe; while the other path enters a DIC detector through a second peristaltic pump to measure the DIC concentration of the standard sample; a series of standard solutions of different concentrations from a region of lower solute concentration to higher solute concentra- tion are prepared and measured as required; according to the meas- urement results, a standard curve is automatically generated, and automatic adjustment of the instrument is completed.
According to the present invention, continuous sample injec- tion measurement can be performed, and intermittent standard sam- ple addition measurement can also be set as required.
The steps for the intermittent standard sample addition meas- urement are as follows: after a certain number of samples are measured by program control, the valve position is switched from the seawater sample inlet to the standard sample inlet by switch-
ing the three-way valve, so as to realize the injection of stand- ard samples; after the standard sample measurement is completed, the valve position of the three-way valve is automatically switched to the seawater sample inlet, so as to continue the auto- 5 matic measurement of seawater, thereby realizing the automatic switching detection of samples and standard samples.
The advantageous effects achieved by the technical solution of the present invention with respect to the prior art are as fol- lows: the present invention uses a liquid dispenser and a low-flow pH and DIC detection technology to realize the synchronous online detection of multiple parameters of seawater acidification, and realize the automatic measurement of a standard curve and the au- tomatic adjustment of an instrument, so as to solve the problems of single parameter, complex system and low degree of automation in traditional seawater acidification measurement; the present in- vention achieves high-precision, automatic detection of multi- parameter (pH, DIC, temperature, salinity) of seawater acidifica- tion, and is particularly suitable for automatic observation of multi-parameter for underway seawater acidification.
The pure water required by the DIC detector is provided by a water purifier through a constant flow pump, and the waste water generated by the DIC detector is recycled through the water puri- fier without additional reagent consumption, thus saving energy and protecting environment.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic structural diagram of the present in- vention;
Reference numerals in the accompanying drawings:
Seawater filter 1; Standard liquid storage tank 2; Three-way valve 3; Standard sample inlet 3A; Seawater sample inlet 3B; Liq- uid dispenser 4; First peristaltic pump 5; Flow-through cell 6; pH probe 7; pH probe detection circuit 8; Second peristaltic pump 9;
DIC detector 10; Constant flow pump 11; Water purifier 12; Data acquisition and control chip 13; Computer 14.
DETAILED DESCRIPTION OF THE EMBODIMENTS
To make the technical problems, technical solutions and bene- ficial effects to be solved by the present invention clearly and obviously, the present invention is further described in detail below with reference to the accompanying drawings and embodiments.
As shown in FIG. 1, the present embodiment comprises a sea- water filter 1, a standard liquid storage tank 2, a three-way valve 3, a liquid dispenser 4, a first peristaltic pump 5, a flow- through cell 6, a pH probe 7, a pH probe detection circuit 8, a second peristaltic pump 9, a DIC detector 10, a constant flow pump 11, a water purifier 12, a data acquisition and control chip 13 and a computer 14;
Sample outlets of the seawater filter 1 and the standard liq- uid storage tank 2 are respectively connected to sample inlets of the three-way valve 3, a sample outlet of the three-way valve 3 is connected to a sample inlet of the liquid dispenser 4, two sample outlets of the liquid dispenser 4 are respectively connected to sample inlets of the first peristaltic pump 5 and the second peri- staltic pump 9, a sample outlet of the first peristaltic pump 5 is connected to a sample inlet of the flow-through cell 6, and a sam- ple outlet of the second peristaltic pump 9 is connected to a sam- ple inlet of the DIC detector 10; the water purifier 12 is con- nected to the carrier sample inlet of the DIC detector 10 via the constant flow pump 11, and the carrier sample outlet of the DIC detector 10 is connected to the water purifier 12, so that pure water generated by the water purifier 12 serves as a carrier for detection of DIC, and the carrier waste liquid after measurement is recycled by the water purifier 12.
The pH probe 7 extends into the flow-through cell 6, and the pH probe 7 is electrically connected to the pH probe detection circuit 8; the circuits of the three-way valve 3, the first peri- staltic pump 5, the second peristaltic pump 9, the pH probe detec- tion circuit 8, the DIC detector 10, the constant flow pump 11 and the water purifier 12 are all connected to the data acquisition and control chip 13, which is connected to the computer 14 so as to control the automatic sampling and detection of the instrument via the data acquisition and control chip 13.
A parameter measurement method for the underway multi- parameter seawater acidification observer comprises the following steps: 1) before the seawater sample is measured, the standard curve is made and the instrument is calibrated: firstly, the valve posi- tion of the three-way valve 3 is switched to the standard sample inlet 3A by a control system, after the standard solution enters the three-way valve 3 through a standard solution storage tank 2, the standard sample is divided into two paths through a liquid dispenser 4, wherein one path enters a flow-through cell 6 through a first peristaltic pump 5, and parameters such as pH, temperature and salinity of the standard sample are measured by a pH probe 7; while the other path enters a DIC detector 10 through a second peristaltic pump 9 to measure the DIC concentration of the stand- ard sample; a series of standard solutions of different concentra- tions from a region of lower solute concentration to higher solute concentration are prepared and measured as required; according to the measurement results, a standard curve is automatically gener- ated, and automatic adjustment of the instrument is completed; 2) after completing the automatic measurement of the standard curve, the seawater sample is measured: the valve position of the three-way valve 3 is switched to the seawater sample inlet 3B for sample injection, firstly, the seawater sample passes through a filter to remove suspended seawater particles, and the seawater sample is divided into two paths via a liquid dispenser 4, wherein one path is conveyed to a flow-through cell 6 by a first peristal- tic pump 5, and parameters such as pH, temperature and salinity of the sample are measured by a pH probe 7, and the other path is conveyed to a DIC detector 10 by a second peristaltic pump 9 to measure a DIC concentration of the sample; the detection time in- terval of the pH probe 7 and the DIC detector 10 are set as re- quired, so as to realize the synchronous measurement of different parameters.
According to the present invention, continuous sample injec- tion measurement can be performed, and intermittent standard sam- ple addition measurement can also be set as required.
The steps for the intermittent standard sample addition meas-
urement are as follows: after a certain number of samples are measured by program control, the valve position is switched from the seawater sample inlet 3B to the standard sample inlet 3A by switching the three-way valve 3, so as to realize the injection of standard samples; after the standard sample measurement is com- pleted, the valve position of the three-way valve 3 is automati- cally switched to the seawater sample inlet 3B, so as to continue the automatic measurement of seawater, thereby realizing the auto- matic switching detection of samples and standard samples.
In the present invention, the pure water is automatically generated by a water purifier, and the measurement process is au- tomatically controlled, which has the advantages of realizing high-precision automatic detection of seawater acidification pa- rameters, performing automatic measurement of standard samples and instrument adjustment at the same time, having less required sam- ple amount and no need of extra reagent consumption, realizing the multi-parameters unattended automatic operation of seawater acidi- fication in a true sense, ensuring long-term stable operation in complex underwater observations, and being particularly suitable for long-time continuous automatic observation of underwater sea- water pH and DIC or long-term unattended online observation in the field.

Claims (2)

CONCLUSIESCONCLUSIONS 1. Waarnemer voor lopend onderzoek naar multiparameter zeewater- verzuring, gekenmerkt doordat deze omvat een zeewaterfilter, een standaard vloeistofopslagtank, een driewegklep, een vloeistofdis- penser, een eerste peristaltische pomp, een doorstroomcel, een pH- sonde, een pH-sonde detectiecircuit, een tweede peristaltische pomp, een DIC-detector, een pomp met constante stroom, een water- zuiveraar, een data-acquisitie- en controlechip en een computer; waarbij monsteruitlaten van het zeewaterfilter en de standaard vloeistofopslagtank respectievelijk zijn aangesloten op de mon- sterinlaten van de driewegklep, waarbij een monsteruitlaat van de driewegklep is aangesloten op een monsterinlaat van de vloeistof- dispenser, waarbij twee monsteruitlaten van de vloeistofdispenser respectievelijk zijn aangesloten op monsterinlaten van de eerste peristaltische pomp en de tweede peristaltische pomp, waarbij een monsteruitlaat van de eerste peristaltische pomp is aangesloten op een monsterinlaat van de doorstroomcel, en waarbij een monsteruit- laat van de tweede peristaltische pomp is aangesloten op een mon- sterinlaat van de DIC-detector; waarbij de waterzuiveraar is aan- gesloten op een dragermonsterinlaat van de DIC-detector via een pomp met constante stroom; waarbij de pH-sonde uitsteekt in de doorstroomcel en de pH-sonde elektrisch is verbonden met een pH- sonde detectiecircuit; waarbij de driewegklep, de eerste peristal- tische pomp, de tweede peristaltische pomp, het detectiecircuit van de pH-sonde, de DIC-detector, de pomp met constante stroom en het circuit van de waterzuiveraar allemaal zijn verbonden met een data-acquisitie- en controlechip, en de data-acquisitie- en con- trolechip is verbonden met een computer om de automatische bemon- stering en detectie van het instrument via de data-acquisitie- en controlechip te regelen.1. Observer for ongoing multiparameter seawater acidification research, characterized by comprising a seawater filter, a standard liquid storage tank, a three-way valve, a liquid dispenser, a first peristaltic pump, a flow cell, a pH probe, a pH probe detection circuit, a second peristaltic pump, a DIC detector, a constant current pump, a water purifier, a data acquisition and control chip and a computer; wherein sample outlets of the seawater filter and the standard liquid storage tank are respectively connected to the sample inlets of the three-way valve, wherein a sample outlet of the three-way valve is connected to a sample inlet of the liquid dispenser, wherein two sample outlets of the liquid dispenser are respectively connected to sample inlets of the first peristaltic pump and the second peristaltic pump, wherein a sample outlet of the first peristaltic pump is connected to a sample inlet of the flow cell, and wherein a sample outlet of the second peristaltic pump is connected to a sample inlet of the DIC detector ; wherein the water purifier is connected to a carrier sample inlet of the DIC detector via a constant flow pump; wherein the pH probe extends into the flow cell and the pH probe is electrically connected to a pH probe detection circuit; wherein the three-way valve, the first peristaltic pump, the second peristaltic pump, the pH probe detection circuit, the DIC detector, the constant flow pump and the water purifier circuit are all connected to a data acquisition and control chip, and the data acquisition and control chip is connected to a computer to control the automatic sampling and detection of the instrument through the data acquisition and control chip. 2. Waarnemer voor lopend onderzoek naar multiparameter zeewater- verzuring volgens conclusie 1, met het kenmerk, dat: de drager- monsteruitlaat van de DIC-detector is aangesloten op de waterzui- veraar om de gemeten dragerafvalvloeistof te recyclen.An observer for ongoing multi-parameter seawater acidification research according to claim 1, characterized in that: the carrier sample outlet of the DIC detector is connected to the water purifier to recycle the measured carrier waste liquid.
NL2031224A 2022-03-09 2022-03-09 Underway multi-parameter seawater acidification observer NL2031224B1 (en)

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